The kinetics, products, and reaction pathways of triclosan/free chlorine reactions were investigated for the pH range 3.5-11. Although pH dependent speciation occurs in both triclosan and free chlorine, only the reaction between HOCl and the phenolate-triclosan was found to play a significant role in the kinetics. The second order rate constant for the reaction between phenolate-triclosan and HOCl was found to be 5.40 (±1.82) Ã 103 M⁻¹s⁻¹. Three chlorinated triclosan intermediates were tentatively identified based on mass spectral analysis. Additionally, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and chloroform formed under excess free chlorine conditions. The majority of the chloroform formed during the reactions does not form via 2,4-dichlorophenol and 2,4,6-trichlorophenol oxidation. Therefore, the majority of chloroform is likely formed via the oxidation of triclosan's phenolic ring. Based on the identified products, a reaction pathway was proposed for the oxidation of triclosan in the presence of free chlorine. / Master of Science

Studies were conducted to explore the interactions among rye grass, chlorophenols and microorganisms. The objectives were to examine some of the processes by which plants affect the fate of subsurface organic contaminants. The research was divided into three studies: interactions between live grasses and 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP), and pentachlorophenol (PCP); physico-chemical interactions between the three chlorophenols and root tissue; and effect of root exudates on biodegradation of TCP. To study the interactions between plants and organic contaminants, rye grass plants were grown in solutions containing DCP, TCP or PCP for one to three weeks. The grass removed substantial amounts of the chlorophenols throughout the incubation time. The majority of each chlorophenol removed from solution could not be recovered by non-destructive solvent extraction. The removal of the chlorophenols from solution and the unrecoverability of the removed compound followed different kinetics, indicating that the two are different processes. Both contaminant removal and unrecoverability were closely related to root surface area but not to transpiration. A qualitative model was developed to describe the uptake of organic contaminants by plants. The data demonstrate the importance of physico-chemical interactions between contaminants and roots and suggest that maximization of root surface area should be one consideration when selecting a plant species for phytoremediation. To study the physico-chemical interactions between plant roots and organic contaminants, the distribution of DCP, TCP and PCP within a three phase system was examined. The three phases were severed grass roots, water and an organic solvent, either hexane or ethyl acetate. The chlorophenol mass that partitioned into the solvent phase was inversely correlated with root mass and root surface area index. Partition coefficients calculated with respect to the organic liquid phase were inversely correlated with root mass and root surface area index. A similar partitioning experiment was conducted using PCP placed in a solution containing only the dissolved organic material released by roots. These resulting partition coefficients decreased with increasing organic carbon concentration. It appeared that the organic compounds released into solution by the roots affected the movement of the chlorophenol into the organic liquid phase. It is proposed that the presence of roots simultaneously promoted retention of the chlorphenols in the aqueous phase and provided a sorption site. The effect of grass root exudates and glucose on the lag time associated with 2,4,6-trichlorophenol (TCP) degradation by an unacclimated microbial inoculant and an acclimated microbial inoculant was investigated. The presence of an alternate organic carbon source reduced lag time for both the acclimated microbial inoculant and the inoculant that had not been previously exposed to chlorinated phenols. The lag time for acclimation of microbes to TCP mineralization was affected by the ratio of the alternate organic carbon source concentration to the biomass concentration. It is proposed that the presence of a readily available, alternate organic carbon source affected lag time through promotion of microbial population growth and provision of a preferred source of carbon and energy. The results indicate that rye grass may directly, through partitioning and uptake, and indirectly, through soil microbes, affect the fate of chlorophenols in the subsurface environment. / Ph. D.

O reservatório de Salto Grande está localizado na região do Município de Americana do Estado de São Paulo. Encontra-se hipereutrofizado, em estágio avançado de contaminação e, em conseqüência, causa diversos problemas sócio-econômicos. Parte da Bacia Hidrográfica do rio Piracicaba, os aportes principais de poluentes são de origens doméstica e industrial, além dos gerados pela lixiviação de áreas agrícolas da bacia. Dentre os contaminantes, há fenóis nas cargas remanescentes das principais indústrias, destacando-se as indústrias químicas, cujos produtos manufaturados são corantes e matérias primas do segmento Nylon. O estudo sobre a distribuição qualitativa e quantitativa de clorofenóis nos sedimentos e nas águas do reservatório é importante devido a seus efeitos tóxicos e persistência. Este trabalho visou determinar os clorofenóis (pentaclorofenol, triclorofenol e diclorofenol) por cromatografia gasosa (CG/DCE), em amostras coletadas em quatro estações no reservatório, no período seco (maio e junho/98) e no período chuvoso (novembro/98 e fevereiro/99). Além disso, foram determinados algumas variáveis físico-químicas do sistema (temperatura, oxigênio dissolvido, turbidez, condutividade, pH, material em suspensão, carbono orgânico, teor de umidade do sedimento), nas mesmas estações, como também foram consideradas as condições climatológicas da área do reservatório e suas variáveis hidráulicas e morfométricas. As etapas para as análises cromatográficas envolveram extração dos clorofenóis das amostras de água por extração líquido-líquido, e estudo do método de extração mais adequado dos clorofenóis das amostras de sedimentos (ultra-som, Soxhlet e agitação). Nas condições estudadas, os valores de clorofenóis das amostras de água e de sedimento encontram-se na faixa de 0,010 a 0,022 &#956g/L, na água e inferiores a 0,50 &#956g/Kg no sedimento. Pelas variáveis analisadas, bem como pelos resultados obtidos, possivelmente vários fatores influíram na disponibilidade desses compostos para o meio, como pH, material em suspensão, carbono orgânico dissolvido, radiação solar e precipitação, removendo-os do meio por absorção, fotólise, diluição e degradação microbiana. Pelos resultados encontrados nas análises cromatográficas, as concentrações dos clorofenóis na água desse reservatório estão abaixo do limite exigido por lei, 0,10 &#956g/L. / Salto Grande reservoir, an important municipal water system located in the region of municipal district of Americana, State of São Paulo, has a history of water quality deterioration as the result of cultural eutrophication. In consequence, noticeable social and economical problems occurred. Wastewater eftluents, domestic and industrial eftluents and lixiviate of agricultural areas, discharged in the Piracicaba watershed are the main contribution of reservoir pollutants. Industrial pollutants can be phenols present in the remaining loads of certain industries, standing out the chemical industries, whose manufactured products are coloring and matters as the segment Nylon, The studies on qualitative and quantitative distribution of chlorophenols in the sediments and waters of Salto Grande reservoir it is important due to its toxicant effects and persistence. This work aimed to determine the chlorophenols (pentachlorophenol, trichlorophenol and dichlorophenol) for gas chromatographic (CG/DCE) in samples collected in four stations in the reservoir, during a dry season (May and June/98) and rainy period (November/98 and February/99). Physical-chemical parameters (temperature, dissolved oxygen, turbidity, conductivity, pH, suspension material, organic carbon, sediment humidity) were determined, and climatological conditions, hydraulic variables and morphological data were considered as well. Chromatographics analyses were doneafter extraction of chlorophenols using liquid-liquid extraction method for water samples and three different methods of extraction of chlorophenols from the sediments samples, ultra-sound, Soxhlet and agitation. Under studied conditions, the values of chlorophenols from water and sediment samples were respectively in the range of 0,010 to 0,022 &#956g/L and inferior of 0,50 &#956g/Kg. Several factors could be influenced the presence of chlorophenols in the samples, such as pH, suspension material, dissolved organic carbon, solar radiation and precipitation, by stimulation of adsorption, light degradation, dilution and microbial degradation. Considered the technical analyses applied, chromatographic analyses of chlorophenols showed concentrations in the water of Salto Grande reservoir below the limit demanded by law, 0,10 &#956g/L.

Neste trabalho foram preparados eletrodos de óxidos de composição nominal Ti/RuyTi(1-y-x)SnxO2 por decomposição térmica (400 °C) via três rotas diferentes: Método Tradicional empregando-se precursores inorgânicos dissolvidos em Isopropanol (MT/ISO) e em solução de HCl 1:1 (v/v) (MT/HCl) e, Método dos Precursores Poliméricos (MPP). Os recobrimentos de óxidos foram caracterizados por Microscopia Eletrônica de Varredura, análises de Energia Dispersiva de raios X e Difração de Raios X. A caracterização eletroquímica dos eletrodos foi feita por estudos de potencial em circuito aberto, tempo de vida útil e voltametria cíclica na ausência e na presença do poluente selecionado como modelo, o 4-clorofenol. Eletrólises do 4-clorofenol e de seus principais subprodutos foram realizadas em uma célula de fluxo tipo filtro-prensa e monitoradas por análises de Cromatografia Líquida de Alta Eficiência, Carbono Orgânico Total e íons cloreto em solução, além de testes bacteriológicos de toxicidade. Os resultados mostram que o método de preparação influencia na morfologia e na composição dos eletrodos, mas não afeta o tamanho dos cristalitos. Apesar das características distintas, MT/ISO e MPP são adequados para o preparo desses eletrodos pois evitam perdas dos componentes e proporcionam recobrimentos de estabilidade eletroquímica bastante apropriada frente às condições drásticas de eletrólise, viabilizando assim a aplicação destes eletrodos na degradação de poluentes orgânicos. Além disso, todos os eletrodos investigados são muito promissores para a degradação eletroquímica de clorofenóis, pois apresentam excelente atividade para o consumo do 4-clorofenol. Independente da composição e do método de preparação do eletrodo, os subprodutos formados na eletrooxidação de 4-clorofenol são: hidroquinona, benzoquinona, cloro-hidroquinona e 4-clorocatecol, além dos ácidos oxálico, maleico, málico, succínico e malônico. Embora a mineralização completa do poluente não tenha sido atingida, a toxicidade das soluções após o término das eletrólises diminui consideravelmente, visto que tanto o composto orgânico de partida quanto os subprodutos aromáticos formados são degradados com excelente eficiência, sobretudo quando se utilizam ânodos preparados por MT/ISO. / In this work oxides electrodes of nominal composition Ti/RuyTi(1-y-x)SnxO2 were prepared by thermal decomposition (400 °C) by three different routes: Traditional Method using inorganic precursors dissolved in either Isopropanol (MT/ISO) or a solution of HCl 1:1 (v/v) (MT/HCl) and the Polymeric Precursors Method (MPP).Oxides coatings were characterized by Scanning Electron Microscopy, Energy Dispersive X ray analyses and X ray Diffraction. The electrochemical characterization of the electrodes was performed by studies of potential in open circuit, service lifetime, and cyclic voltammetry in the absence and in the presence of the model pollutant 4-chlorophenol. Electrolyses of 4-chlorophenol and its main by-products were accomplished in filter-press flow cell and monitored by High Performance Liquid Chromatography, Total Organic Carbon, and analyses of chloride ions in solution, besides bacteriological toxicity tests. Results show that the preparation method influences the morphology and composition of the electrodes, but it does not affect the crystallite size. In spite of their different characteristics, MT/ISO and MPP are appropriate methods for the preparation of these electrodes because they avoid the loss of components and provide electrochemically stable coatings before the drastic conditions of electrolysis. Therefore, these electrodes can be applied in the degradation of organic pollutants. Furthermore, all the investigated electrodes are very promising for the electrochemical degradation of chlorophenols, because they present excellent activity regarding the consumption of 4-chlorophenol. Independent of the composition and the preparation method of the electrode, the by-products formed in the electrooxidation of 4-chlorophenol are hydroquinone, benzoquinone, chlorohydroquinone, and 4-chlorocatechol, as well as oxalic, maleic, malic, succinic, and malonic acids. Although the complete mineralization of the pollutant has not been reached, the toxicity of the solutions decreases considerably after the end of the electrolyses. This is because both the initial organic compound and the aromatic by-products formed in the electrolyses are degraded with excellent efficiency, especially when the anodes prepared by MT/ISO are employed.

Nos últimos anos, os processos oxidativos avançados (POAs) têm emergido como métodos potencialmente poderosos para transformar poluentes orgânicos recalcitrantes em substâncias menos tóxicas. O presente trabalho visa estudar a degradação de clorofenóis 2,4-diclorofenol (2,4-DCF) e pentaclorofenol (PCF) em solução aquosa por meio do processo foto-Fenton. Os experimentos foram realizados em um reator fotoquímico, em regime batelada, com recirculação e admissão contínua de peróxido de hidrogênio. Os efeitos das concentrações iniciais de clorofenóis, H2O2 e Fe(II), bem como, da potência da lâmpada de vapor de mercúrio, foram estudados a partir de um planejamento experimental Doehlert em multiplos níveis e analisados segundo a metodologia de superfícies de respostas. A foto-oxidação foi monitorada por medidas da concentração de carbono orgânico total (TOC) e do espectro de absorção da solução ao longo do tempo e, em alguns casos, medidas de toxicidade por meio de bioensaios com Artemia sp. Os resultados dos experimentos realizados com 2,4-DCF evidenciaram degradação gradativa, com remoções de TOC superiores a 99%, após 1 hora de tratamento, além de remoção de toxicidade, mesmo para altas concentrações iniciais do poluente (até ca. 415 mgC L-1). Nos experimentos realizados com PCF observouse decaimento inicial de TOC bastante rápido (15 minutos), o que sugere que a degradação dos clorofenóis torna-se mais rápida com o aumento do número de átomos de cloro ligados ao anel aromático. Foi removida mais da metade do TOC inicial por volta de 30 minutos de reação, obtendo-se remoções de até 90,8% ao final do tratamento. Por outro lado, comparado ao 2,4-DCF, no caso do PCF observou-se redução acentuada da taxa de remoção de TOC após esse tempo, o que pode ser explicado a partir da maior concentração de íons cloreto em solução, da formação de complexo estável desses íons com Fe(III) e de espécies geradas a partir de reações envolvendo esse complexo. No conjunto, os resultados comprovam a viabilidade do processo foto-Fenton para remediação de efluentes aquosos contendo clorofenóis. / In recent years, advanced oxidation processes (AOP) have emerged as potentially powerful methods to transforming organic pollutants into harmless substances. The present work aims to study the degradation of chlorophenols (2,4-dichlorophenol and pentachlorophenol) in aqueous solution by the photo-Fenton process. The experiments were conducted in a batch recycle photochemical reactor with continuous feed of hydrogen peroxide solution. The effects of the initial concentrations of chlorophenols, H2O2, and Fe(II), as well as of the electric power of mercury vapor lamp, were studied by means of a Doehlert multivariate experimental design at multiple levels. Experimental results were analyzed according to the response surface methodology. In order to characterize the degradation of the pollutant, time-measurements of the total organic carbon concentration (TOC) as well as the absorbance spectra of the solution, were carried out. In some cases toxicity bioassays were carried out with Artemia sp. The results obtained from experiments with 2,4-dichlorophenol showed a gradual degradation, with more than 99% of TOC removals after 1 hour of treatment, along with toxicity removal, even for high initial pollutant concentrations (ca. 415 mgC L-1). In the case of pentachlorophenol, a fast initial TOC decrease (around 15 minutes) was observed, suggesting that chlorophenols degradation becomes faster with the increment of chloro atoms number bounded to the aromatic ring. More than a half of the initial TOC was removed around 30 minutes of reaction, rising 90.8% of TOC removal at the end of the treatment. In the other hand, comparing to 2,4-DCF, for PCF a marked reduction of the maximum rate of TOC removal after that time. This can be explained by higher concentrations of chloride ions in the solution, for the formation of stable complexes with Fe(III) ion and resulting species in reaction involving such complexes. As a whole, the results confirm the effectiveness of the photo-Fenton process for the remediation of aqueous solutions containing chlorophenols.

O reservatório de Salto Grande está localizado na região do Município de Americana do Estado de São Paulo. Encontra-se hipereutrofizado, em estágio avançado de contaminação e, em conseqüência, causa diversos problemas sócio-econômicos. Parte da Bacia Hidrográfica do rio Piracicaba, os aportes principais de poluentes são de origens doméstica e industrial, além dos gerados pela lixiviação de áreas agrícolas da bacia. Dentre os contaminantes, há fenóis nas cargas remanescentes das principais indústrias, destacando-se as indústrias químicas, cujos produtos manufaturados são corantes e matérias primas do segmento Nylon. O estudo sobre a distribuição qualitativa e quantitativa de clorofenóis nos sedimentos e nas águas do reservatório é importante devido a seus efeitos tóxicos e persistência. Este trabalho visou determinar os clorofenóis (pentaclorofenol, triclorofenol e diclorofenol) por cromatografia gasosa (CG/DCE), em amostras coletadas em quatro estações no reservatório, no período seco (maio e junho/98) e no período chuvoso (novembro/98 e fevereiro/99). Além disso, foram determinados algumas variáveis físico-químicas do sistema (temperatura, oxigênio dissolvido, turbidez, condutividade, pH, material em suspensão, carbono orgânico, teor de umidade do sedimento), nas mesmas estações, como também foram consideradas as condições climatológicas da área do reservatório e suas variáveis hidráulicas e morfométricas. As etapas para as análises cromatográficas envolveram extração dos clorofenóis das amostras de água por extração líquido-líquido, e estudo do método de extração mais adequado dos clorofenóis das amostras de sedimentos (ultra-som, Soxhlet e agitação). Nas condições estudadas, os valores de clorofenóis das amostras de água e de sedimento encontram-se na faixa de 0,010 a 0,022 &#956g/L, na água e inferiores a 0,50 &#956g/Kg no sedimento. Pelas variáveis analisadas, bem como pelos resultados obtidos, possivelmente vários fatores influíram na disponibilidade desses compostos para o meio, como pH, material em suspensão, carbono orgânico dissolvido, radiação solar e precipitação, removendo-os do meio por absorção, fotólise, diluição e degradação microbiana. Pelos resultados encontrados nas análises cromatográficas, as concentrações dos clorofenóis na água desse reservatório estão abaixo do limite exigido por lei, 0,10 &#956g/L. / Salto Grande reservoir, an important municipal water system located in the region of municipal district of Americana, State of São Paulo, has a history of water quality deterioration as the result of cultural eutrophication. In consequence, noticeable social and economical problems occurred. Wastewater eftluents, domestic and industrial eftluents and lixiviate of agricultural areas, discharged in the Piracicaba watershed are the main contribution of reservoir pollutants. Industrial pollutants can be phenols present in the remaining loads of certain industries, standing out the chemical industries, whose manufactured products are coloring and matters as the segment Nylon, The studies on qualitative and quantitative distribution of chlorophenols in the sediments and waters of Salto Grande reservoir it is important due to its toxicant effects and persistence. This work aimed to determine the chlorophenols (pentachlorophenol, trichlorophenol and dichlorophenol) for gas chromatographic (CG/DCE) in samples collected in four stations in the reservoir, during a dry season (May and June/98) and rainy period (November/98 and February/99). Physical-chemical parameters (temperature, dissolved oxygen, turbidity, conductivity, pH, suspension material, organic carbon, sediment humidity) were determined, and climatological conditions, hydraulic variables and morphological data were considered as well. Chromatographics analyses were doneafter extraction of chlorophenols using liquid-liquid extraction method for water samples and three different methods of extraction of chlorophenols from the sediments samples, ultra-sound, Soxhlet and agitation. Under studied conditions, the values of chlorophenols from water and sediment samples were respectively in the range of 0,010 to 0,022 &#956g/L and inferior of 0,50 &#956g/Kg. Several factors could be influenced the presence of chlorophenols in the samples, such as pH, suspension material, dissolved organic carbon, solar radiation and precipitation, by stimulation of adsorption, light degradation, dilution and microbial degradation. Considered the technical analyses applied, chromatographic analyses of chlorophenols showed concentrations in the water of Salto Grande reservoir below the limit demanded by law, 0,10 &#956g/L.

Biological cells and subcellular organelles are surrounded by membranes to form compartments performing specialized functions. Adsorption or partitioning of biologically active compounds into the membrane is the first step in the process of modification of cell function. This work is concerned with the problem of distribution of charged molecules between water and electrically charged membrane surface and between water and octanol. Part I of this thesis is focused on the electrostatic interactions taking place between charges on the membrane and ions present in the aqueous region of the membrane/water interface. The objective was to explore theoretically the origin of anomalous behavior of Ruthenium Red (RuR), a positively charged hexavalent ion. It was discovered in studies of RuR adsorption to negatively charged membranes that within the framework of the Gouy-Chapman theory of the membrane/water interface, RuR behaves as an ion with effective charge less than its physical charge. Moreover, the effective charge was found to be dependent on the density of electric charge at the membrane surface. Two theoretical models of the interfacial region were examined: the Rod Model and the Maximum Density Model. The Rod Model takes into account steric constraints imposed on RuR at the vicinity of the membrane surface. The Maximum Density Model attempts to account for non-ideal behavior by including repulsive interactions. These theoretical studies illustrate the consequences of finite size and ion-ion interactions of adsorption of large molecular ions to electrically charged membrane surfaces. Part II is an experimental study whose objective was to determine the partition coefficient of the negatively charged 2,3,4,5-tetrachlorophenol (TeCP) between water and octanol. The study was based on spectrophotometric measurements of the equilibrium concentrations of TeCP in water and octanol as a function of pH. The octanol/water partition coefficient for both the non-ionized and ionized species of TeCP were determined. It was found that the partition coefficient of ionized TeCP to lipid membrane is about 400 times greater than that for octanol. This result supports the hypothesis that the octanol/water partition coefficient of ionized chlorophenols cannot be used for predicting their distribution between water and lipid-bilayercontaining elements of the environment.

Naturally occurring plant derived phenols can be degraded through bacteria in swine waste. Chlorinated phenols, which are not naturally present in the environment, are toxic and generated from industrial activities as such petrochemical, pharmaceutical, plastic, rubber, pesticide, iron, steel, paper production, coal conversion, wood preserving, and cellulose bleaching. Large scale coal gasification and carbonization plants are another source of chlorinated phenols. Although not normally present in the environment, chlorinated phenols are structurally similar to many plant derived phenolics. It is our hypothesis that bacteria located in swine wastes may also have the ability to degrade chlorinated phenols. Identifying situations (and organisms) in which degradation of pollutants occurs is important field of research. Experimental work was focused on measuring the degradation of seven chlorinated phenols in swine waste using solid-phase micro-extraction (SPME) and gas chromatography(GC). Microbes in the waste perform respiration or fermentation to obtain the energy they need to carry out their life processes. Fermentation is a process in which electrons are transferred from one organic substrate to another and which results in incomplete degradation of organic compounds. Anaerobic respiration is a process in which organic substrates are degraded completely to CO2, but using substances other than oxygen as the terminal electron acceptor (such as Fe(III), NO3- or SO42-). Anaerobic respiration using these alternative electron acceptors provides an easier pathway for degradation of aromatics than fermentation alone. Usually the abundance of these electron acceptors in waste is low since microbes consume them readily and thus they must be added to the mixture. Our work focused on development of methods for the quantification of chlorinated phenols in swine wastes and results of bioremediation research. In this study, chlorophenols were extracted by SPME and analysed by GC. This research project mainly focused on the anaerobic degradation of chlorophenols in swine waste. It was observed that the decreased concentration of the chlorophenols was likely due to partitioning of the chlorophenols to solids, sticking to glass bottles and by bacteria present in the swine waste. In summary, it was observed that by ANOVA and gas production analysis 2,6-dichlorophenol and 2,4,5-trichlorophenol were likely to be degraded by bacteria present in swine waste.

Diss. (sammanfattning) Stockholm : Karolinska institutet, 2006. / Härtill 6 uppsatser.

Thesis (M.S.)--University of Michigan, 1971.